Ethyl Bromide → 1-ethylsulfanyl-4-fluorobenzene

Temperature

25 °C

To a stirred solution of 4-fluorobenzenethiol (80 g, 0.625 mol) and bromoethane (71.88 g, 0.666 mol) in DMF (1.25 L) under nitrogen atmosphere, Cs2CO3 (213.75 g, 0.666 mol) was added. The reaction mixture was stirred at 25° C. overnight. TLC (petroleum ether) indicated the reaction was complete. The mixture was diluted with water (800 mL), extracted with ethyl acetate (600 mL×3). The combined organic layers were washed with water (500 mL×2) and brine (500 mL), dried over Na2SO4 and concentrated in vacuum to give ethyl(4-fluorophenyl)sulfane (60 g, 61.5%) as a colorless oil. A mixture of ethyl(4-fluorophenyl)sulfane (60 g, 0.38 mol), acetic acid (1 L) and 30% H2O2 (180 mL) was stirred at reflux under N2 overnight. TLC (petroleum ether:ethyl acetate=4:1) indicated the reaction was complete. After cooled to room temperature, the reaction mixture was poured into water (500 mL). Then NaHSO3 (200 g) was add. The mixture was extracted with ethyl acetate (500 mL×3), dried over Na2SO4 and concentrated in vacuum to remove the remaining acetic acid. Then the residue was poured into saturated aq. NaOH (800 mL) and extracted with ethyl acetate (500 mL×3) again. The organic layer was dried over Na2SO4 and concentrated in vacuum to give the title compound (66 g, 92.4%) as a colorless liquid.

1. extractionextracted with ethyl acetate (600 mL×3)
2. washThe combined organic layers were washed with water (500 mL×2) and brine (500 mL)
3. dry with materialdried over Na2SO4
4. concentrationconcentrated in vacuum

ORD record

ord-9f55f8ba52ee4dfaa4278a7cf82fc6f4

Source dataset

uspto-grants-2012_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08119624B2